Synthesis, Modification, and Application of Siloxane Materials for Environmental Sensing

As human populations and resource consumption increase, it is increasingly important to monitor the quality of our environment. While laboratory instruments offer useful information, portable, easy to use sensors would allow environmental analysis to occur on-site, at lower cost, and with minimal operator training. We explore the synthesis, modification, and applications of modified polysiloxane in environmental sensing. Multiple methods of producing modified siloxanes were investigated. Oligomers were formed by using functionalized monomers, producing siloxane materials containing silicon hydride, methyl, and phenyl side chains. Silicon hydride-functionalized oligomers were further modified by hydrosilylation to incorporate methyl ester and naphthyl side chains. Modifications to the siloxane materials were also carried out using post-curing treatments. Methyl ester-functionalized siloxane was incorporated into the surface of a cured poly(dimethylsiloxane) film by siloxane equilibration. The materials containing methyl esters were hydrolyzed to reveal carboxylic acids, which could later be used for covalent protein immobilization. Finally, the siloxane surfaces were modified to incorporate antibodies by covalent, affinity, and adsorption-based attachment. These modifications were characterized by a variety of methods, including contact angle, attenuated total reflectance Fourier transform infrared spectroscopy, dye labels, and 1H nuclear magnetic resonance spectroscopy. The modified siloxane materials were employed in a variety of sensing schemes. Volatile organic compounds were detected using methyl, phenyl, and naphthyl-functionalized materials on a Fabry-Perot interferometer and a refractometer. The Fabry-Perot interferometer was found to detect the analytes upon siloxane extraction by deformation of the Bragg reflectors. The refractometer was used to determine that naphthyl-functionalized siloxanes had elevated refractive indices, rendering these materials more sensitive to some analytes. Antibody-modified siloxanes were used to detect biological analytes through a solid phase microextraction-mediated enzyme linked immunosorbent assay (SPME ELISA). The SPME ELISA was found to have higher analyte sensitivity compared to a conventional ELISA system. The detection scheme was used to detect Escherichia coli at 8500 CFU/mL. These results demonstrate the variety of methods that can be used to modify siloxanes and the wide range of applications of modified siloxanes has been demonstrated through chemical and biological sensing schemes.

Understanding arsenic mobility and speciation in lake sediments impacted by ore roasting near Giant mine, NWT

The roasting of gold-bearing arsenopyrite at Giant mine (Northwest Territories) between 1949 and 1999 released approximately 20,000 tonnes of toxic arsenic-bearing aerosols in the local aerial environment. Detailed examination of lake sediments, sediment porewaters, surface waters and lake hydrology sampled from three lakes of differing limnological characteristics was conducted in summer and winter conditions. Samples were analyzed for solid and dissolved elemental concentrations, speciation and mineralogy. The three lakes are located less than 5km from the mine roaster, and downwind, based on predominant wind direction. The objective of the study was to assess the controls on the mobility and fate of arsenic in these roaster-impacted subarctic lacustrine environments. Results show that the occurrence of arsenic trioxide in lake sediments coincides with the regional onset of industrial activities. The bulk of arsenic in sediments is contained in the form of secondary sulphide precipitates, with iron oxides hosting a minimal amount of arsenic near the surface-water interface. The presence of geogenic arsenic is likely contained as dilute impurities in common rock-forming minerals, and is not believed to be a significant source of arsenic to sediments, porewaters or lake waters. Furthermore, the well correlated depth-profiles of arsenic, antimony and gold in sediments may help reveal roaster impact. The soluble arsenic trioxide particles contained in sediments act as the primary source of arsenic into porewaters. Dissolved arsenic in reducing porewaters both precipitate as secondary sulphides in situ, and diffuse upwards into the overlying lake waters. Arsenic diffusion out of porewaters, combined with watercourse-driven residence time, are estimated to be the predominant mechanisms controlling arsenic concentrations in overlying lake waters. The sequestration of arsenic from porewaters as sulphide precipitates, in the study lakes, is not an effective process in keeping lake-water arsenic concentrations below guidelines for the protection of the freshwater environment and drinking water. Seasonal impacts on lake geochemistry derive from ice covering lake waters, cutting them off from of atmospheric oxygen, along with the exclusion of solutes from the ice. Such effects are limited in deep lakes but are can be an important factor controlling arsenic precipitation and mobility in ponds.